JPH0830865B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic material capable of rapid processing, less dye contamination, and high sharpness. It relates to a photosensitive material.

[Prior art]

Generally, in the method of forming a color image using a silver halide color photographic light-sensitive material, after imagewise exposure, an oxidized P-phenylenediamine color developing agent and a dye image-forming coupler are reacted to form a color image. are doing. In this method, the color reproduction method by the normal color reduction method is applied, and red,
Cyan, magenta, and yellow dye images corresponding to green and blue are formed on the respective photosensitive layers. In recent years, when forming color images like this,
In order to shorten the development processing time, high temperature development processing and labor saving of processing steps are generally performed. In particular, in order to reduce the development processing time by high-temperature development, it is extremely important to increase the development speed in color development. The development speed in color development is affected from two aspects. One is a silver halide color photographic light-sensitive material, and the other is a color developing solution. In the former case, the shape, size, and halogen composition of the grains of the photosensitive silver halide emulsion used have a large effect on the development rate, and in the latter case, the conditions of the color developer, especially the type of development inhibitor, are affected. It has been found that it is susceptible, and in particular silver chloride grains exhibit remarkably high development rates under certain conditions.

With silver halide color photographic light-sensitive materials in which the silver halide consists essentially of silver chloride, rapid processing is possible, and development is completed even if the development time is 90 seconds or less, but there is a new drawback that dye contamination easily occurs after processing. Was found.

As a result of various studies on this dye contamination, the anti-irradiation dye added to the light-sensitive material was insufficient in the outflow and decolorization to the processing solution during short-time processing,
It was found that the photosensitive material remained after the processing.

Therefore, it is possible to reduce the amount of the anti-irradiation dye used to prevent dye contamination, but in this case,
The original purpose of the anti-irradiation dye is to deteriorate the sharpness.

As described above, in a silver halide color photographic light-sensitive material containing silver halide grains substantially composed of silver chloride, a dye image that can be processed rapidly, has less dye stain, and has high sharpness is obtained. There are various problems to be solved for formation, and there is a very high demand for a silver halide color photographic light-sensitive material satisfying all of these problems.

[Problems to be solved by the invention]

The present invention has been made in view of the above, and it is technically possible to provide a silver halide color photographic light-sensitive material capable of rapid processing, having good sharpness, and having less dye stain after development processing. It is an issue.

[Means for solving problems]

A silver halide color photographic light-sensitive material of the present invention which solves the above technical problem is a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a reflective support. a silver halide color photographic material having photographic constituent layers including, in at least one layer of the photographic constituent layers, the compound 1mg / m ² ~8mg / m ² containing represented by the following general formula [I], And at least one of the light-sensitive silver halide emulsion layers contains silver halide grains containing 95 mol% or more of silver chloride, and 3.0 g in the reflective support.
It is characterized by containing titanium oxide in an amount of / m ² or more.

General formula [I] [In the formula, R and R'may be the same or different and each represent a cyano group, a carboxyl group or an alkoxycarbonyl group, and Z and Z'may be the same or different and each is hydrogen. Represents an atom, sodium, potassium, lithium, and n and m may be the same or different and each represents 1 or 2. ) [Specific Structure of the Invention] Hereinafter, the structure of the present invention will be described more specifically.

The photosensitive silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention contains silver halide grains containing silver chloride in an amount of 95 mol% or more, and preferably has a silver chloride content of 100 mol%. is there. This silver halide emulsion can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less, preferably 5 mol% or less. When silver iodide is present, it is usually 1 mol% or less, preferably 0.5 mol%
It is below, most preferably 0%. Such a silver halide grain substantially consisting of silver chloride according to the present invention has a silver halide grain content of 80% by weight based on all the silver halide grains in the silver halide emulsion layer.
% Or more, and more preferably 100%.

The silver halide color photographic light-sensitive material of the present invention can be composed of two or more light-sensitive silver halide emulsion layers. At least one of the two or more light-sensitive silver halide emulsion layers needs to be a silver halide emulsion layer containing silver halide grains consisting essentially of silver chloride. The composition of silver halide in the other photosensitive silver halide emulsion layers is not particularly limited, but it must contain silver chlorobromide grains and silver chloroiodide grains containing at least 50 mol% of silver chloride. Is preferred. The amount of silver bromide and silver iodide in the silver halide color photographic light-sensitive material of the present invention is
It is preferably about 30 mol% or less, more preferably about 10 mol% or less, based on the total silver halide emulsion.

These silver halides can be produced by any of the ammonia method, the neutral method, the acidic method, etc., and also by the simultaneous mixing method, the forward mixing method, the back mixing method, the convergence method, etc. It may be one that has been processed.

The crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure having different inside and outside. In addition, silver halide is a surface latent image type that forms a latent image mainly on the surface,
It may be of an internal latent image type which mainly forms a latent image inside the grain.

Further, the silver halide emulsion of the present invention comprises a noble metal salt such as ruthenium, rhodium, palladium, iridium, platinum and gold (for example, ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadite, potassium chloroaurate, etc.). Noble metal sensitization, activated gelatin, sulfur sensitization with unstable sulfur (eg sodium thiosulfate), selenium sensitization with selenium compounds, reduction sensitization with stannous salts, polyamines, thiourea dioxide, etc. and low pAg. Can be applied.

Further, these silver halide emulsions can be optically sensitized by using various sensitizing dyes in order to impart photosensitivity in a desired light-sensitive wavelength region. Preferred sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes.

Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus. , Quinoline nucleus, etc. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

Examples of useful sensitizing dyes used in a blue-sensitive silver halide emulsion layer include West German Patent 929,080 and U.S. Patent 2,231,6.
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
Examples thereof include those described in No. 3,694,217, No. 4,025,349, No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, No. 52-24844 and the like. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908, and 2,
Representative examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes such as those described in 739,149, 2,945,763 and British Patent 505,979. Further, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 4, No. 2,270,378, No. 2,442,710, No. 2,454,629,
Cyanine dyes such as those described in No. 2,776,280,
Typical examples thereof include merocyanine dyes and complex cyanine dyes. Furthermore, US Patent 2,
213,995, 2,493,748, 2,519,001, West German patent 9
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in No. 29,080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. Typical examples are Japanese Examined Japanese Patent Publications No. 43-4932, No. 43-4933, No. 43-4936 and No. 4
4-32753, 45-25831, 45-26474, 46-11627
No. 46, No. 46-18107, No. 47-8741, No. 47-11114, No. 47-
25379, 47-37443, 48-28293, 48-38406,
48-38407, 48-38408, 48-41203, 48-412
04, 49-6207, 50-40662, 53-12375, 5
4-34535, 55-1569, JP-A-50-33220, 50-338
No. 28, No. 50-38526, No. 51-107127, No. 51-115820, No.
51-135528, 51-151527, 52-23931, 52-519
No. 32, No. 52-104916, No. 52-104917, No. 52-109925
No. 52-110618, 54-80118, 56-25728, 5
7-1483, 58-10753, 58-91445, 58-153926
No. 59, 114-533, 59-116645, 59-116647,
U.S. Patents 2,688,545, 2,977,229, 3,397,060
No., No. 3,506,443, No. 3,578,447, No. 3,672,898,
No. 3,679,428, No. 3,769,301, No. 3,814,609, No. 3,
837,862 etc.

Examples of dyes that are used together with sensitizing dyes and have no spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization include, for example, aromatic organic acid formaldehyde condensation products. (For example, US Pat.
437,510), a cadmium salt, an azaindene compound, an aminostilbene compound substituted with a nitrogen-containing heterocyclic group (for example, US Pat. Nos. 2,933,390 and 3,635,721).
Those listed in No.). U.S. Patent 3,615,613,
The combinations described in 3,615,641, 3,617,295 and 3,635,721 are particularly useful.

The amount of the compound represented by formula (I) used in the present invention ranges from ^{1mg / m 2 ~8mg / m 2} , more preferably from ^{2mg / m 2 ~5mg / m 2} . Used amount is 1mg / m ²
In the following, we cannot prevent the irritation,
Sharpness deteriorates. On the other hand, when it is 8 mg / m ² or more, especially in rapid processing, the decolorizing property is insufficient and color contamination occurs.

Specific examples of the anti-irradiation dye represented by the general formula [I] used in the present invention are shown below, but the invention is not limited thereto.

The support used in the present invention is a white pigment.
A reflective support containing 3.0 g / m ² or more of titanium oxide. Here, such titanium oxide may be rutile type or anatase type, and the present invention also includes titanium oxide whose surface is coated with a metal oxide such as hydrated alumina and hydrated ferrite.

As the reflective support usually used for printing materials,
A paper laminated with an α-olefin polymer such as polyethylene is used, but in the present invention, it is preferable that the α-olefin polymer layer contains titanium oxide.

If the weight of titanium oxide is 3.0 g / m ² or more, the effect of the present invention can be obtained, but it is preferably 3.5 g / m ² or more, and more preferably 4.0 g / m ² or more. Although also improved sharpness accordance weight of titanium oxide is increased, 10 g / m ² or more in order to slight and the increase in manufacturing cost problems improve sharpness by titanium oxide increase occurs, 10 g / m ² or more The inclusion is not preferable in terms of cost.

The particle size of titanium oxide used in the present invention is not particularly limited, but an average particle size of 0.05 μm to 10 μm is preferable,
0.1 μm to 0.5 μm is particularly preferable.

The silver halide photographic light-sensitive material of the present invention contains an antifoggant for the purpose of preventing fog during storage with time and during development.
Stabilizers can be added.

Antifoggants and stabilizers include U.S. Pat.
No. 2,743,180, pentazaindenes described in 2,743,181, U.S. Patents 2,716,062, 2,444,607,
2,44,605, 2,756,147, 2,835,581, 2,8
52,375, Research Disclosure (Research D
isclosure) 14851 tetrazaindenes,
Triazaindenes described in US Pat. No. 2,772,164 and azaindenes such as polymerized azaindenes described in JP-A-57-211142; US Pat. No. 2,131,03
U.S. Pat. Nos. 3,342,596 and 3,954,478, thiazolium salts, U.S. Pat. No. 3,148,067, pyrilium salts, and Japanese Patent Publication No. 50-40665; quaternary onium salts such as phosphonium salts; Patent 2,403,927,
3,266,897, 3,708,303, JP-A-55-135835,
Mercaptotetrazoles described in 59-71047,
Mercaptotriazoles, mercaptodiazoles,
Mercaptothiazoles described in U.S. Pat.No. 2,824,001, mercaptobenzthiazoles described in U.S. Pat.No. 3,397,987, mercaptobenzimidazoles,
Mercaptooxadiazoles described in US Pat. No. 2,843,491, mercapto-substituted heterocyclic compounds such as mercaptothiadiazoles described in US Pat. No. 3,364,028; catechol described in US Pat. No. 3,236,652, Japanese Patent Publication No. 43-10256 , Resorcins described in JP-B-56-44413, and polyhydroxybenzenes such as gallic acid esters described in JP-B-43-4133; West German Patent 1,
189,380 tetrazole, U.S. Pat.
Triazoles described in 7,509, U.S. Patent 2,704,
Benztriazoles described in 721, U.S. Pat.
Urazols described in 87,135, U.S. Patent 3,106,46
Pyrazoles described in No. 7, indazoles described in U.S. Pat.No. 2,271,229, and azoles such as polymerized benztriazoles described in JP-A-59-90844 and U.S. Pat.No. 3,161,515 Pyrimidines,
Heterocyclic compounds such as 3-pyrazolidones described in U.S. Pat.No. 2,751,297, and polymerized pyrrolidones described in U.S. Pat. Same as 140445
No., UK Patent 1,356,142, U.S. Patent 3,575,699, 3,
Various inhibitor precursors described in 649, 267, etc .;
Sulfinic acids and sulfonic acid derivatives described in US Pat. No. 3,047,393; US Pat. Nos. 2,566,266 and 2,839,405
No. 2,488,709, No. 2,728,663, and the like.

As the binder (or protective colloid) of the silver halide emulsion according to the present invention, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose Hydrophilic colloids such as derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used.

When gelatin is used as the binder (or protective colloid) of the silver halide emulsion according to the present invention, the jelly strength of gelatin is not limited, but the jelly strength is preferably 250 g or more (value measured by the buggy method).

A photographic emulsion layer of a silver halide light-sensitive material according to the present invention,
Other hydrophilic colloid layers can be hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and enhance film strength.
The hardener can be added in an amount such that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the silver halide light-sensitive material according to the present invention for the purpose of enhancing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

In the color development processing, the emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) to form a dye. Dye forming couplers are used. The dye-forming couplers are usually selected such that for each emulsion layer a dye is formed that absorbs the light in the sensitive spectrum of the emulsion layer, with the blue-sensitive emulsion layer containing a yellow dye-forming coupler and a green dye-forming coupler. A magenta dye-forming coupler is used in the light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group having carbon atoms of 8 or more, which makes a coupler called a ballast group non-diffusible in the molecule. Further, these dye-forming couplers are required to reduce 4 molecules of silver ions because one molecule of dye is formed. Even if they are 4 equivalents, 2 molecules of silver ions need only be reduced to 2 equivalents. It may be sexually mixed. Dye-forming couplers include development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners, fog agents, antifoggants, and chemical sensitizers by coupling with an oxidized product of a developing agent. , Spectral sensitizers, and compounds that release photographically useful fragments such as desensitizers. These dye-forming couplers are color couplers that have the effect of color correction, or DI that releases a development inhibitor with development and improves image sharpness and image graininess.
The R coupler may be used in combination as long as the effect of the present invention is not impaired. At this time, the DIR coupler is preferably the same type of dye formed from the dye-forming coupler used in the same emulsion layer as the dye formed from the coupler, but when the color turbidity is not conspicuous, a different type of DIR coupler is used. Those that form a dye may be used. In place of the DIR coupler, a coupling reaction with the oxidant of the developing agent in combination with or in combination with the coupler,
Releases development inhibitors at the same time as producing colorless compounds
You may use a DIR compound in the range which does not impair the effect of this invention.

DIR couplers and DIR compounds that may be used in combination include those in which the inhibitor is directly bonded at the coupling position and the inhibitor is 2
Those linked to the coupling position via a valent group so that the inhibitor is released by an intramolecular nucleophilic reaction in the group that has left due to the coupling reaction or an intramolecular electron transfer reaction ( Timing DIR coupler and timing D
Referred to as IR compound). Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application. A colorless coupler which performs a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler (yellow coupler) used in the present invention, various acylacetanilide type couplers can be preferably used. Of these,
Benzoyl acetanilide and pivaloyl acetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include British Patent 1,077,874 and Japanese Patent Publication No. 45-40757.
No. 47, No. 47-1031, No. 47-26133, No. 48-94432,
50-87650, 51-3631, 52-115219, 54-994
No. 33, No. 54-133329, No. 56-30127, U.S. Patent 2,875,0
57, 3,253,924, 3,265,506, 3,408,194
Issue 3,551,155, Issue 3,551,156, Issue 3,664,841,
3,725,072, 3,730,722, 3,891,445, 3,9
00,483, 3,929,484, 3,933,500, 3,973,96
No. 8, No. 3,990,896, No. 4,012,259, No. 4,022,620,
4,029,508, 4,057,432, 4,106,942, 4,1
33,958, 4,269,936, 4,286,053, 4,304,84
No. 5, No. 4,314,023, No. 4,336,327, No. 4,356,258,
No. 4,386,155, No. 4,401,752, etc.

Also magenta dye-forming coupler (magenta coupler)
As the above, various 5-pyrazolone-based couplers, pyrazolobenzimidazole-based couplers, pyrazolotriazole-based pyrazoloazole-based couplers, and open-chain acylacetonitrile-based couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used are disclosed in Japanese Patent Application No. 58-164.
882, 58-167326, 58-206321, 58-214863
No. 58, No. 58-217339, No. 59-24653, No. 40-6031,
40-6035, 45-40757, 47-27411, 49-3785
4, JP-A-50-13041, 51-26541, 51-37646
No. 51, No. 51-105820, No. 52-42121, No. 53-123129, No.
53-125835, 53-129035, 54-48540, 56-292
No. 36, No. 56-75648, No. 57-17950, No. 57-35858, No.
57-146251, 59-99437, British Patent No. 1,252,418,
U.S. Patent Nos. 2,600,788, 3,005,712 and 3,062,653
Issue 3,127,269, Issue 3,214,437, Issue 3,253,924,
3,311,476, 3,419,391, 3,519,429, 3,5
No. 58,319, No. 3,582, 322, No. 3,615,506, No. 3,658,5
No. 44, No. 3,705,896, No. 3,725,067, No. 3,758,309
Issue 3,823,156, Issue 3,834,908, Issue 3,891,445,
3,907,571, 3,926,631, 3,928,044, 3,9
35,015, 3,960,571, 4,076,533, 4,133,68
No. 6, No. 4,237,217, No. 4,241,168, No. 4,264,723,
No. 4,301,235, No. 4,310,623, etc.

As the cyan dye-forming coupler (cyan coupler), various naphthol-based couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent Nos. 1,038,331 and 1,543,0.
No. 40, Japanese Patent Publication No. 48-36894, JP-A No. 48-59838, No. 50-137
No. 137, No. 51-146828, No. 53-105226, No. 54-115230
No. 56, No. 56-29235, No. 56-104333, No. 56-126833,
57-133650, 57-155538, 57-204545, 58-11
8643, 59-31953, 59-31954, 59-59656,
59-124341, 59-166956, U.S. Pat.No. 2,369,929
No. 2,423,730, 2,434,272, 2,474,293,
2,698,794, 2,772,162, 2,801,171, 2,8
95,826, 3,253,924, 3,311,476, 3,458,31
No. 5, No. 3,476,563, No. 3,591,383, No. 3,737,316,
No. 3,758,308, No. 3,767,411, No. 3,790,384, No. 3,8
80,661, 3,926,634, 4,004,929, 4,009,0
No. 35, No. 4,012,258, No. 4,052,212, No. 4,124,396
No., 4,134,766, 4,138,258, 4,146,396,
4,149,886, 4,178,183, 4,205,990, 4,2
54,212, 4,264,722, 4,288,532, 4,296,19
No. 9, 4,296,200, 4,299,914, 4,333,999,
4,334,011, 4,386,155, 4,401,752, 4,4
No. 27,767 etc. are described.

Colored couplers include, for example, British Patent No. 937,62.
No. 1, 1,035,959, 1,255,111, JP-A-48-22028
No. 52-42121, Japanese Sho 38-22335, 44-2016,
No. 44-15754, U.S. Patent Nos. 2,449,966, 2,521,908.
No., No. 2,543,691, No. 2,801,171, No. 2,983,608,
3,005,712, 3,034,892, 3,061,432, 3,4
19,391, 3,476,560, 3,476,563, 3,481,74
No. 1, No. 3,519,429, No. 3,583,971, No. 3,622,328,
3,684,514, 4,004,929, 4,070,191, 4,1
38,258, 4,138,264, 4,163,670, 4,292,40
Those described in No. 0 and No. 4,369,248 can be used.

As the DIR coupler, for example, British Patent No. 953,454,
U.S. Pat.Nos. 3,227,554, 3,615,506, 3,617,291
No. 3, No. 3,701,783, No. 3,933,500, No. 4,095,984,
4,149,886, 4,286,054, 4,359,521, JP-A-52-90932, 56-116029, 57-151944 and the like compounds and U.S. Pat.No. 4,248,962, 4,409,323,
JP-A-57-154234, 58-162949, 58-205150,
59-195643, 59-206843, 59-206836, 59-
The timing DIR couplers described in 210440 and 60-7429 can be preferably used.

As the DIR compound, for example, U.S. Patent No. 3,632,345,
3,928,041, 3,938,996, 3,958,993, 3,9
61,959, 4,046,574, 4,052,213, 4,171,22
3, 4,186,012, JP-A-52-65433, 52-130327
No. 57-128335 and the like can be preferably used.

As colorless couplers, U.S. Patent No. 2,998,314 and British Patent No. 1,284,6 for controlling gradation, preventing color turbidity and fogging
So-called Weiss couplers described in Japanese Patent No. 49 and West German Patent 1,168,769 can be used.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant,
A nonionic surfactant and a cationic surfactant can be used.

The emulsion layers of the light-sensitive material of the present invention (the same color-sensitive layers and /
Or different color-sensitive layers), an oxidant of a developing agent or an electron transfer agent migrates to cause color turbidity, deterioration of sharpness, and conspicuous graininess. Can be used.

The antifoggant may be contained in the emulsion layer itself, or may be contained in the intermediate layer by providing an intermediate layer between adjacent emulsion layers.

An image stabilizer which prevents deterioration of a dye image can be used in the silver halide light-sensitive material of the present invention.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer is an ultraviolet absorber to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction and the like, and to prevent deterioration of the image by UV light. May be included.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the silver halide light-sensitive material of the present invention, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. Compounds that can be preferably used as the development accelerator are Research D
isclosure) 17643 Nos. XXI, B to D compounds, and the development retarder is 17643 No. XXI, E compounds. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The photographic emulsion layer of the silver halide light-sensitive material of the present invention comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary quaternary compound for the purpose of increasing sensitivity, increasing contrast or promoting development. It may contain an ammonium compound, a urethane derivative, a urea derivative, an imidazole derivative, or the like.

The silver halide light-sensitive material of the present invention includes a filter layer,
An auxiliary layer such as an antihalation layer and / or an irradiation prevention layer can be provided. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained.

A matting agent can be added to the silver halide emulsion layer and / or other hydrophilic colloid layers of the silver halide light-sensitive material of the present invention for the purpose of reducing gloss of the light-sensitive material, improving writing properties, and preventing sticking of the light-sensitive materials to each other. .

A lubricant may be added to the silver halide light-sensitive material of the present invention to reduce its sliding friction.

An antistatic agent for the purpose of antistatic can be added to the silver halide light-sensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and is a hydrophilic colloid other than the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. It may be used in layers.

The photographic emulsion layer and / or the other hydrophilic colloid layer of the silver halide light-sensitive material of the present invention have a coating property improvement, antistatic property,
Various surfactants can be used for the purpose of improving slipperiness, emulsifying and dispersing, preventing adhesion, improving photographic characteristics (promotion of development, hardening, sensitization, etc.).

The support used in the silver halide light-sensitive material of the present invention includes paper laminated with α-olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer), flexible reflective support such as synthetic paper, acetic acid. Cellulose, cellulose nitrate, polystyrene, polyvinyl chloride,
A flexible support provided with a reflective layer on a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate, polycarbonate, or polyamide, glass, metal, pottery, etc. are included.

The photosensitive material of the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, It may be applied via one or more subbing layers to improve hardness, antihalation properties, friction properties, and / or other properties.

At the time of coating the silver halide light-sensitive material of the present invention during production, a thickener may be used to improve coatability.
For a hardener such as a hardener that causes gelation before coating when it is added to the coating solution in advance because it has a high reactivity, it is recommended to mix it with a static mixer or the like immediately before coating. preferable.

In preparing the silver halide light-sensitive material of the present invention, the silver halide emulsion layer and the other hydrophilic colloid layer are formed by Research Disclosure 176.
It can be applied by the method described in A of XV of No. 43 and dried by the method described in B of the same.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam, X-ray, γ-ray Any of light emitted from a phosphor excited by α-rays or the like can be used.

The exposure time is 0.1 seconds to 1 which is usually used in printers.
The exposure time may be, of course, less than 1 millisecond, for example, an exposure of 100 nanoseconds to 1 millisecond using a cathode ray tube or a xenon flash lamp, or an exposure longer than 1 second or more. The exposure may be performed continuously or intermittently.

Various color developments can be used for the development processing of the light-sensitive material of the present invention. Alternatively, a color image may be formed by the inversion method. When the reversal method is used, a black negative development step is carried out, white exposure is carried out without a fixing processing step, or a bath containing a fogging agent is used for further color development processing. (The process of applying white light exposure or the process of treating with a fogging agent may be the same as the color developing process.) In the present invention, the color developing process is a process of forming a color color image. Specifically, it is a step of forming a color image by a coupling reaction between an oxidized product of a color developing agent and a color coupler.

Therefore, in the color development processing step, it is usually necessary to include a color developing agent in the color developing solution, but the color developing agent is incorporated in the color photographic material, and the color developing solution containing the color developing agent or Treatment with an alkaline solution (activator solution) is also included. The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes aminophenol type and p-phenylenediamine type derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, P-toluenesulfonate, sulfite, oxalate, benzenesulfonate and the like. it can.

These compounds are generally about 0.
It is used at a concentration of 1 g to about 30 g, and more preferably at a concentration of about 1 g to 15 g for color developer 1. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

The processing temperature of the color developing bath is 10 to 65 ° C, preferably 25 to 45 ° C, more preferably 30 to 40 ° C.

Examples of the aminophenol-based developer include o-
Aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4 dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine-based color developing agents are N, N '
-Dialkyl-p-phenylenediamine compound, wherein the alkyl group and the phenyl group may be substituted or unsubstituted. Among them, particularly useful compound examples are N, N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N'-dimethyl-p-phenylenediamine hydrochloride, 2- Amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-amino-3-methyl-NN'-diethylaniline, 4-amino-N- (2-methoxyethyl) -N-
Examples thereof include ethyl-3-methylaniline-p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more kinds. Further, the color developing agent may be incorporated in a color photographic material. For example, US Pat.
A method of incorporating a color developing agent such as 719,492 into a metal salt and incorporating the color developing agent into a Schiff salt as shown in US Pat. No. 3,342,559 and Research Disclosure 1976 No. 15159. Method, a method of incorporating as a dye precursor as shown in JP-A-58-65429 and 58-24137, and a method of incorporating as a color developing agent precursor as shown in U.S. Pat.No. 3,342,597. You can
In this case, the silver halide color photographic light-sensitive material can be treated with an alkaline solution (activator solution) instead of the color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment. The color developing solution used in the present invention may contain an alkaline agent usually used in a developing solution, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. It may further contain various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as ditrazine acid, and preservatives such as hydroxylamine or sulfite. May be. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide can be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or higher,
It is preferably about 9 to 13, more preferably 9.5 to 11.0.

In the color developer used in the present invention, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid and bentose are used as antioxidants. Or hexose, pyrogallol-
It may contain 1,3-dimethyl ether or the like.

Various chelating agents can be used as a sequestering agent in the color developing solution used in the present invention.
For example, ethylenediaminetetraacetic acid as the chelating agent,
Amine polycarboxylic acids such as diethylenetriaminopentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, citric acid or glucone Examples thereof include oxycarboxylic acids such as acids, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

〔Example〕

Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

Example 1 A silver halide color photographic light-sensitive material sample No. 1 was prepared by sequentially coating the following layers on a polyethylene-laminated paper support (titanium oxide content: 2.7 g / m ² ) from the support side. .

Layer 1 ... 1.2 g / m ² gelatin, 0.32 g / m ² (silver equivalent, the same applies below) blue-sensitive silver chlorobromide emulsion (silver chloride content 50 mol%), 0.50 g / m ² dioctyl 0.80 dissolved in phthalate
A layer containing g / m ² of a yellow coupler (Y-1).

Layer 2 ... Intermediate layer comprising 0.7 g / m ² of gelatin and 0.5 mg / m ² of the anti-irradiation dye (I-2) of the present invention.

Layer 3: 1.25 g / m ² gelatin, 0.22 g / m ² green-sensitive silver chlorobromide emulsion (silver chloride content 50 mol%), 0.60 g / m ² dissolved in 0.30 g / m ² dioctyl phthalate A layer containing m ² of magenta coupler (M-1).

Layer 4 ... an intermediate layer consisting of 1.2 g / m ² of gelatin.

Layer 5: 1.40 g / m ² gelatin, 0.20 g / m ² red-sensitive silver chlorobromide emulsion (silver chloride content 50 mol%), 0.40 g / m ² dissolved in 0.20 g / m ² dioctyl phthalate A layer containing m ² of cyan coupler (C-1).

Layer 6 ... 0.30 g / m ² UV absorber (UV- dissolved in 1.0 g / m ² gelatin and 0.20 g / m ² dioctyl phthalate
A layer containing 1).

Layer 7 ... A layer containing 0.50 g / m ² of gelatin.

As a hardener, sodium 2,4-dichloro-6-hydroxy-S-triazine was added to layers 2, 4 and 7 so that the amount was 0.017 per 1 g of gelatin.

Also, the halogen composition of silver halide in Layer 1, Layer 3, and Layer 5 was changed as shown in Table-1, and the type and addition amount of the anti-irradiation dye in Layer 2 were changed as shown in Table-1. Samples No. 2 to No. 20 were prepared by changing the amount of titanium oxide in the body as shown in Table 1.

Each of the above light-sensitive material samples Nos. 1 to 20 was exposed through an optical wedge and then processed in the next step.

Processing step (35 ° C) Color development 45 seconds and 1 minute 15 seconds Bleach fixing 45 seconds Stabilization 1 minute 30 seconds Dry 60-80 ° C 2 minutes The composition of each processing solution is as follows.

Color developer (per 1) Bleaching fixer Stabilizer The maximum density (Dm) and fog (Fog) of the blue-sensitive emulsion layer without using sensitometry were determined for each of the samples after the above treatment.

Further, the degree of dye contamination due to the residual anti-irradiation dye was determined by measuring the optical reflection density at 650 nm of the unexposed portion (white background portion) of each of the treated samples (treatment time of 45 seconds). .

Further, each sample was exposed through a wedge for measuring MTF, and processed by the same process as described above.

The MTF (Modulatio Transfer Function) of the red-sensitive silver halide emulsion layer of each sample after the above treatment was determined by a microdensitometer, and the MTF at a spatial frequency of 5 lines / mm.
The values were compared. It should be noted that the determination of image sharpness by MTF is well known to those skilled in the art, but "The theory of th"
e photographic process 3rd edition ”.

 Table 1 shows the results.

As is clear from Table 1, in Samples No. 1 to No. 3 using the silver halide emulsion having a low silver chloride content, the developing speed is slow and a sufficient maximum density cannot be obtained by a short-time processing.

In contrast, sample No. 4 using silver chloride in the blue-sensitive emulsion layer
~ No. 9 is a sample which obtained a sufficiently high maximum density in a short development time of 1 minute and 15 seconds, and further used silver chloride or silver chlorobromide having a high silver chloride content in all silver halide emulsion layers. No.1
From 0 to No. 20, a sufficient maximum density can be obtained by developing for only 45 seconds.

Next, paying attention to dye stain and sharpness, the samples containing 16 mg / m ^{2 of} anti-irradiation dye show high sharpness but unsatisfactory performance due to large dye stain. Further, the sample with an irradiation prevention dye of 0.5 mg / m ² has low sharpness although it does not stain the dye, and this can be recovered even if the support is replaced with one containing the titanium oxide of the present invention in an amount of 3.0 g / m ² or more. Not a thing (Sample No. 15). On the other hand, titanium oxide content
In 2.7 g / m ^2, the sample specimen No.2,5,11 prevent irradiation dye 4.0 mg / m ^2, the dye stain, show a performance satisfactory substantially even and sharpness, yet in terms of sharpness I have some complaints. On the other hand, the sample of the present invention (Sample No. 8,14,16 to 20) containing 4.0 mg / m ^{2 of the} anti-irradiation dye and further containing titanium oxide of 3.0 g / m ² or more The effectiveness of the present invention is shown by the fact that there is little dye contamination and it has extremely high sharpness.

〔The invention's effect〕

As described above, according to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which is capable of rapid processing, has good sharpness, and has less dye stain after development processing.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-59-168438 (JP, A) JP-A-48-34233 (JP, A) JP-A-48-81521 (JP, A) JP-A-60- 256141 (JP, A) JP 57-64235 (JP, A) JP 58-60738 (JP, A) JP 58-95736 (JP, A) JP 62-32448 (JP, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a reflective support. In at least one of the photographic constituent layers, 1 mg / m 2 of the compound represented by the following general formula [I]
^{2 to} 8 mg / m ² and at least one of the light-sensitive silver halide emulsion layers contains silver halide grains containing 95 mol% or more of silver chloride, and 3.0 g / m ² in the reflective support. A silver halide color photographic light-sensitive material containing titanium oxide of m ² or more. General formula [I] [In the formula, R and R'may be the same or different and each represents a cyano group, a carboxyl group or an alkoxycarbonyl group, and Z and Z'may be the same or different and each is hydrogen. Represents an atom, sodium, potassium, lithium, and n and m may be the same or different and each represents 1 or 2. )